US10994265B2 - Catalyst system for oxidative dehydrogenation, reactor for preparing butadiene including catalyst system, and method of preparing 1,3-butadiene - Google Patents
Catalyst system for oxidative dehydrogenation, reactor for preparing butadiene including catalyst system, and method of preparing 1,3-butadiene Download PDFInfo
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- US10994265B2 US10994265B2 US16/477,866 US201816477866A US10994265B2 US 10994265 B2 US10994265 B2 US 10994265B2 US 201816477866 A US201816477866 A US 201816477866A US 10994265 B2 US10994265 B2 US 10994265B2
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- 239000003054 catalyst Substances 0.000 title claims abstract description 223
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 title claims abstract description 80
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 title abstract description 116
- 238000000034 method Methods 0.000 title abstract description 25
- -1 catalyst system Chemical compound 0.000 title description 2
- 238000010790 dilution Methods 0.000 claims abstract description 41
- 239000012895 dilution Substances 0.000 claims abstract description 41
- 238000000576 coating method Methods 0.000 claims abstract description 31
- 239000011248 coating agent Substances 0.000 claims abstract description 30
- 239000000945 filler Substances 0.000 claims abstract description 30
- 239000000376 reactant Substances 0.000 claims abstract description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 26
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 26
- 229910001308 Zinc ferrite Inorganic materials 0.000 claims description 24
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 24
- WGEATSXPYVGFCC-UHFFFAOYSA-N zinc ferrite Chemical compound O=[Zn].O=[Fe]O[Fe]=O WGEATSXPYVGFCC-UHFFFAOYSA-N 0.000 claims description 24
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000011575 calcium Substances 0.000 claims description 14
- 239000010949 copper Substances 0.000 claims description 14
- 239000011777 magnesium Substances 0.000 claims description 14
- 239000011572 manganese Substances 0.000 claims description 14
- 238000012856 packing Methods 0.000 claims description 14
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 13
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 13
- 239000000377 silicon dioxide Substances 0.000 claims description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 229910052878 cordierite Inorganic materials 0.000 claims description 10
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims description 10
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 claims description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 7
- 229910052684 Cerium Inorganic materials 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052788 barium Inorganic materials 0.000 claims description 7
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052790 beryllium Inorganic materials 0.000 claims description 7
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052791 calcium Inorganic materials 0.000 claims description 7
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- 239000010941 cobalt Substances 0.000 claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 229910052746 lanthanum Inorganic materials 0.000 claims description 7
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- 229910052705 radium Inorganic materials 0.000 claims description 7
- HCWPIIXVSYCSAN-UHFFFAOYSA-N radium atom Chemical compound [Ra] HCWPIIXVSYCSAN-UHFFFAOYSA-N 0.000 claims description 7
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 claims description 7
- 229910052712 strontium Inorganic materials 0.000 claims description 7
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 94
- 239000004480 active ingredient Substances 0.000 abstract description 8
- 230000007774 longterm Effects 0.000 abstract description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 40
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 40
- 230000000052 comparative effect Effects 0.000 description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 230000000694 effects Effects 0.000 description 17
- 239000000843 powder Substances 0.000 description 17
- 230000020169 heat generation Effects 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 239000008188 pellet Substances 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 9
- 238000007086 side reaction Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 7
- 239000012153 distilled water Substances 0.000 description 7
- 238000009826 distribution Methods 0.000 description 6
- 230000003247 decreasing effect Effects 0.000 description 5
- 238000011049 filling Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 230000000750 progressive effect Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- IAQRGUVFOMOMEM-ARJAWSKDSA-N cis-but-2-ene Chemical compound C\C=C/C IAQRGUVFOMOMEM-ARJAWSKDSA-N 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
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- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C11/00—Aliphatic unsaturated hydrocarbons
- C07C11/12—Alkadienes
- C07C11/16—Alkadienes with four carbon atoms
- C07C11/167—1, 3-Butadiene
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
- C07C5/3332—Catalytic processes with metal oxides or metal sulfides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/42—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
- C07C5/48—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor with oxygen as an acceptor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
- C07C2521/04—Alumina
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/74—Iron group metals
- C07C2523/745—Iron
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with zinc, cadmium or mercury
Definitions
- the present invention relates to a catalyst system for oxidative dehydrogenation, a reactor for preparing butadiene including the catalyst system, and a method of preparing 1,3-butadiene. More specifically, the present invention relates to a catalyst system for oxidative dehydrogenation, wherein a coating catalyst having a porous support coated with an active ingredient is diluted with a dilution filler and a reactor is filled with the diluted catalyst, or a reactor is filled with a catalyst for oxidative dehydrogenation so that the concentration of an active ingredient included in the catalyst gradually increases in the direction from reactants inlet in which reactants are fed into the reactor to products outlet. According to the catalyst system of the present invention, heat generated inside a reactor can be efficiently controlled, whereby conversion rate, selectivity, and yield can be greatly improved and long-term stability of a catalyst can be improved.
- 1,3-butadiene a major basic product of petroleum fraction, is a representative raw material used in preparation of synthetic rubber, and the price thereof fluctuates rapidly in connection with supply and demand of the petrochemical industry.
- methods of preparing 1,3-butadiene include naphtha cracking, direct dehydrogenation of normal butene, oxidative dehydrogenation of normal butene, and the like.
- the method of preparing 1,3-butadiene by oxidative dehydrogenation of normal butene, butene and oxygen react in the presence of a metal oxide catalyst to generate 1,3-butadiene and water.
- water generated as a result of the reaction is stable.
- the method is thermodynamically very advantageous.
- oxidative dehydrogenation of normal butene is an exothermic reaction unlike direct dehydrogenation, reaction can be performed at a low temperature.
- 1,3-butadiene can be obtained in high yield while reducing energy consumption.
- an oxidizing agent since an oxidizing agent is added, the generation amount of carbon deposits which shorten catalyst life by poisoning the catalyst is reduced. Further, since removal of the oxidizing agent is easy, the method of preparing 1,3-butadiene using oxidative dehydrogenation is very suitable for commercialization.
- Patent Document 1 KR 10-1508776 B1
- the present invention has been made in view of the above problems, and it is one object of the present invention to provide a catalyst system for oxidative dehydrogenation capable of effectively controlling heat generated inside a reactor to prevent catalyst deterioration, thereby improving conversion rate, selectivity, and yield.
- a catalyst system for oxidative dehydrogenation wherein a reactor is filled with a catalyst for oxidative dehydrogenation in an n-layer structure (n being an integer of 2 or more), wherein the catalyst is diluted and the reactor is filled with the diluted catalyst so that each layer of the n-layer structure satisfies Equations 1 and 2 below.
- X represents a content of AB 2 O 4 and is 3 to 30, wherein A is one or more selected from the group consisting of copper (Cu), radium (Ra), barium (Ba), strontium (Sr), calcium (Ca), beryllium (Be), zinc (Zn), magnesium (Mg), manganese (Mn), cerium (Ce), zirconium (Zr), lanthanum (La), and cobalt (Co) and B is iron (Fe); Y is a content of a porous support and is 20 to 97; and Z is a content of one or more dilution fillers selected from alumina, silica, silicon carbide, zirconia, titania, and cordierite and is 0 to 77.
- X n >X n ⁇ 1 , [Equation 2]
- X n represents X for the n-th layer
- X n ⁇ 1 represents X for the (n ⁇ 1)th layer
- a catalyst system for oxidative dehydrogenation wherein a reactor is filled with a catalyst for oxidative dehydrogenation, wherein the catalyst is diluted and the reactor is filled with the diluted catalyst so as to satisfy Equation 6 below.
- X is a content of AB 2 O 4 and is 5 to 25, wherein A is one or more selected from the group consisting of copper (Cu), radium (Ra), barium (Ba), strontium (Sr), calcium (Ca), beryllium (Be), zinc (Zn), magnesium (Mg), manganese (Mn), cerium (Ce), zirconium (Zr), lanthanum (La), and cobalt (Co) and B is iron (Fe); Y is a content of a porous support and is 25 to 85; and Z is a content of one or more selected from alumina, silica, silicon carbide, zirconia, titania, and cordierite and is 10 to 70.
- A is one or more selected from the group consisting of copper (Cu), radium (Ra), barium (Ba), strontium (Sr), calcium (Ca), beryllium (Be), zinc (Zn), magnesium (Mg), manganese (Mn), cerium (Ce),
- a reactor for preparing butadiene including the catalyst system for oxidative dehydrogenation.
- a method of preparing 1,3-butadiene including performing oxidative dehydrogenation using the reactor for preparing butadiene of the present invention, wherein the oxidative dehydrogenation is performed while continuously passing reactants containing a C4 compound including normal butene through the catalyst bed of the reactor.
- the present invention advantageously provides a catalyst system for oxidative dehydrogenation, wherein a catalyst having a porous support on which an active ingredient is uniformly and firmly coated is diluted in a dilution filler and a reactor is filled with the diluted catalyst, or a reactor is filled with a catalyst for oxidative dehydrogenation so that the concentration of an active ingredient included in the catalyst gradually increases in the direction from reactants inlet in which reactants are fed into the reactor to products outlet.
- the catalyst system according to the present invention it is possible to effectively control distribution of heat generated inside a reactor during oxidative dehydrogenation without adding a separate apparatus or changing the conventional manufacturing facilities, and thus to improve conversion rate, selectivity, and yield.
- catalyst deterioration can be reduced, thereby improving long-term stability of a catalyst.
- FIG. 1 is a graph showing temperature distribution inside a catalyst bed when oxidative dehydrogenation is performed using the catalyst system according to Example 1.
- FIG. 2 is a graph showing temperature distribution inside a catalyst bed when oxidative dehydrogenation is performed using the catalyst system according to Additional Comparative Example 3.
- a catalyst for oxidative dehydrogenation is diluted to satisfy Equation 1 below, and a reactor is filled with the diluted catalyst.
- X represents a content of AB 2 O 4 and is 3 to 30, wherein A is one or more selected from the group consisting of copper (Cu), radium (Ra), barium (Ba), strontium (Sr), calcium (Ca), beryllium (Be), zinc (Zn), magnesium (Mg), manganese (Mn), cerium (Ce), zirconium (Zr), lanthanum (La), and cobalt (Co) and B is iron (Fe); Y is a content of a porous support and is 20 to 97; and Z is a content of one or more dilution fillers selected from alumina, silica, silicon carbide, zirconia, titania, and cordierite and is 0 to 77.
- X n >X n ⁇ 1 , [Equation 2]
- X n represents X for the n-th layer
- X n ⁇ 1 represents X for the (n ⁇ 1)th layer
- AB 2 O 4 is the active ingredient of a catalyst
- the catalyst for oxidative dehydrogenation is a coating catalyst having a porous support coated with the active ingredient AB 2 O 4 .
- AB 2 O 4 can be a zinc ferrite (ZnFe 2 O 4 ), wherein A is zinc (Zn) and B is iron (Fe).
- the catalyst can exhibit excellent activity in oxidative dehydrogenation of normal butene, and can have high selectivity for 1,3-butadiene.
- AB 2 O 4 can have an average particle diameter of 0.1 to 250 ⁇ m, 10 to 200 ⁇ m, 15 to 150 ⁇ m, 15 to 100 ⁇ m, 15 to 60 ⁇ m, or 25 to 60 ⁇ m. Within this range, coating of the active ingredient on the porous support can be easily performed, and the catalyst can have excellent activity, thereby improving reaction efficiency.
- AB 2 O 4 having an average particle diameter within the above range can be selected, for example, using a sieving method.
- Equation 1 X is preferably 3 to 30, 3 to 27, 3.5 to 20, 3.5 to 18, or 3.5 to 14. Within this range, reaction efficiency can be excellent, thereby improving yield, selectivity, and conversion rate.
- the porous support can have an average particle diameter of 3 to 7 mm or 4 to 6 mm. Within this range, reaction efficiency can be excellent, thereby improving conversion rate and selectivity.
- the porous support can have an average pore size of 50 to 200 ⁇ m or 100 to 150 ⁇ m. Within this range, coating of AB 2 O 4 powder can be easy performed and desorption of the powder can be prevented.
- the average particle diameter and average pore size of the porous support can be measured, for example, using a method of calculating a surface area and an average pore size through adsorption isotherm of nitrogen by the BET method and the BJH (Barret-Joyner-Halenda) method, respectively, or using a mercury impregnation method.
- the porous support can have a packing density of 0.8 to 1.5 kg/m 3 or 0.9 to 1.3 kg/m 3 . Coating rate is determined based on the packing density.
- the porous support has a packing density within this range, separation or desorption of the AB 2 O 4 powder can be prevented, and the support can be easily coated with the powder. Further, when oxidative dehydrogenation is performed, the conversion rate of butene or 1,3-butadiene yield can be increased, and excessive increase in the temperature inside a catalyst bed can be suppressed, thereby increasing thermal stability.
- packing density is calculated by dividing mass capable of filling a tubular measuring cylinder to 100 cc by a volume value of 100 cc thereof.
- the porous support is preferably spherical, hollow, or in the form of pellets.
- reaction efficiency can be excellent, thereby improving yield, selectivity, and conversion rate.
- spherical, pellet, and hollow shapes are not particularly limited as long as they are within the ordinary range of those skilled in the art of porous support technology, and these shapes are clearly distinguished.
- the porous support can be one or more selected from the group consisting of alumina, silica, titania, zirconia, silicon carbide, and cordierite, and is preferably alumina or silica. In this case, mechanical strength for filling a reactor is satisfied and side reaction can be reduced.
- the porous support is alumina.
- mechanical strength can be ensured, and butadiene yield and selectivity can be prevented from being lowered by side reaction during oxidative dehydrogenation.
- Equation 1 Y can be 20 to 97, 21 to 90, 21 to 86, 30 to 86, or 40 to 86. Within this range, catalytic activity and heat generation control can be excellent.
- the coating catalyst of the present invention can further include an organic/inorganic binder when necessary.
- the binder can be included in an amount of 30 parts by weight or less, 0.1 to 20 parts by weight, or 0.1 to 10 parts by weight based on 100 parts by weight of AB 2 O 4 . Within this range, the abrasion resistance of the catalyst can be improved without significantly lowering the efficiency of oxidative dehydrogenation.
- the binder can include aluminum-silicate, methylcellulose, hydroxypropyl methylcellulose, or both.
- the binder is contained in an appropriate amount, the abrasion resistance of the catalyst can be improved without significantly lowering the efficiency of oxidative dehydrogenation.
- the coating catalyst of the present invention can be a binder-free catalyst.
- side reaction is not caused by the binder, the conversion rate of normal butene and selectivity for butadiene can be greatly increased.
- introduction of some components is omitted, a process of preparing the catalyst can be simplified, thereby reducing process costs.
- binder-free means that an organic or inorganic binder is omitted when preparing a catalyst and/or that a catalyst is prepared without the binder.
- a fixed-bed reactor can be filled with the catalyst for oxidative dehydrogenation according to the present invention in a 2- to 8-layer, 3- to 8-layer, 3- to 6-layer, or 3- to 5-layer structure.
- distribution of heat generated inside the reactor can be effectively controlled without significantly increasing process costs.
- conversion rate, selectivity, and yield can be greatly improved, and long-term stability of the catalyst can be improved.
- the catalyst system of the present invention satisfies Equation 3 below.
- Equation 3 the catalyst system of the present invention satisfies Equation 3 below.
- X n ⁇ X n ⁇ 1 conversion rate, selectivity, yield, and long-term stability of the catalyst can be improved.
- X n represents X for the n-th layer
- X n ⁇ 1 represents X for the (n ⁇ 1)th layer
- At least one of the n layers can have a Z value greater than 0.
- the dilution filler can be, for example, one or more selected from alumina, silica, silicon carbide, zirconia, titania, and cordierite, and is preferably one or more selected from alumina and silica. In this case, it is possible to suppress generation of excessive reaction heat while minimizing side reaction, thereby greatly improving the efficiency of oxidative dehydrogenation.
- the catalyst system of the present invention satisfies Equation 4 below when at least one layer has a Z value other than 0. In this case, excessive temperature increase of the catalyst bed due to excessive heat may be suppressed, and thus productivity such as conversion rate, selectivity, and yield can be greatly improved when butadiene is prepared. ( Yn ⁇ Yn ⁇ 1) ⁇ 15, [Equation 4]
- Y n represents Y for the n-th layer
- Y n ⁇ 1 represents Y for the (n ⁇ 1)th layer
- Equation 5 Equation 5 below.
- heat generation due to oxidative dehydrogenation can be effectively controlled so that the activity or stability of the catalyst can be continuously maintained high and reaction efficiency can be improved.
- Z n represents Z for the n-th layer
- Z n ⁇ 1 represents Z for the (n ⁇ 1)th layer
- a reactor is filled with the catalyst for oxidative dehydrogenation in an n-layer structure (n being an integer of 2 or more).
- the catalyst is diluted and the reactor is filled with the diluted catalyst so that each layer satisfies Equations 1 and 2.
- the porous support has a packing density of 0.8 to 1.5 kg/m 3 or 0.9 to 1.2 kg/m 3 .
- separation or peeling of AB 2 O 4 powder from the porous support can be prevented, and the support can be uniformly and firmly coated with the catalyst.
- heat generation inside the catalyst bed during oxidative dehydrogenation can be effectively controlled, and side reaction can be suppressed, thereby improving the conversion rate of butene, butadiene yield, and selectivity.
- a reactor is filled with the catalyst for oxidative dehydrogenation in a three-layer structure.
- the catalyst is diluted and the reactor is filled with the diluted catalyst so that each layer satisfies Equations 1 and 2 below.
- Equations 1 and 2 With respect to the direction in which reactants are fed into the reactor, in the case of the first layer, X is 3.5 to 7; Y is 21.5 to 43; and Z is 50 to 75, in the case of the second layer, X is 7 to 10.5; Y is 43 to 64.5; and Z is 25 to 50, and in the case of the third layer, X is 13 to 18; Y is 82 to 87; and Z is 0 to 5.
- X is a content of zinc ferrite powder wherein A is Zn and B is Fe, Y is a content of a porous support, and Z is a content of one or more dilution fillers selected from alumina, silica, silicon carbide, and zirconia, wherein the porous support is alumina having a packing density of 0.8 to 1.5 kg/m 3 .
- X n >X n ⁇ 1 , [Equation 2]
- X n represents X for the n-th layer
- X n ⁇ 1 represents X for the (n ⁇ 1)th layer
- n is the total number of layers and is 3.
- X is 3 to 4.5; Y is 20 to 35; and Z is 60.5 to 77, in the second layer, X is 5 to 8; Y is 40 to 50; and Z is 45 to 55, and in the third layer, X is 10 to 16; Y is 60 to 90; and Z is 0 to 30.
- oxidative dehydrogenation is performed using the catalyst system, side reaction can be suppressed, and the conversion rate of butene, selectivity for butadiene, and yield can be improved.
- the catalyst for oxidative dehydrogenation is diluted and a reactor is filled with the catalyst so as to satisfy Equation 6 below.
- X is a content of AB 2 O 4 and is 5 to 25, wherein A is one or more selected from the group consisting of copper (Cu), radium (Ra), barium (Ba), strontium (Sr), calcium (Ca), beryllium (Be), zinc (Zn), magnesium (Mg), manganese (Mn), cerium (Ce), zirconium (Zr), lanthanum (La), and cobalt (Co) and B is iron (Fe); Y is a content of a porous support and is 25 to 85; and Z is a content of one or more dilution fillers selected from alumina, silica, silicon carbide, zirconia, titania, and cordierite and is 10 to 70.
- A is one or more selected from the group consisting of copper (Cu), radium (Ra), barium (Ba), strontium (Sr), calcium (Ca), beryllium (Be), zinc (Zn), magnesium (Mg), manganese (Mn),
- Equation 6 X is preferably 5 to 25, 7 to 20, 7 to 18, 7 to 14, 7 to 13.5, or 7 to 11. Within this range, reaction efficiency can be excellent, thereby improving yield, selectivity, and conversion rate.
- Equation 6 Y can be, for example, 25 to 85, 35 to 80, 36 to 75, 36.5 to 70, 36.5 to 60, or 40 to 50. Within this range, catalytic activity and catalyst stability can be maintained high, and the productivity of butadiene can be increased.
- Z can be, for example, 10 to 70, 20 to 70, or 40 to 60. Within this range, excessive heat generation due to oxidative dehydrogenation can be effectively suppressed, thereby improving catalyst stability and reaction efficiency.
- the porous support can have a packing density of 0.8 to 1.5 kg/m 3 or 0.9 to 1.2 kg/m 3 .
- the mechanical strength of the coating catalyst can be excellent, and separation or peeling of AB 2 O 4 powder from the porous support can be prevented.
- heat generation in the catalyst bed during oxidative dehydrogenation can be effectively suppressed, and butadiene yield and selectivity for butadiene can be improved.
- the catalyst system can be an oxidative-dehydrogenation catalyst system for preparation of 1,3-butadiene.
- the present invention provides a reactor for preparing butadiene including the catalyst system and a method of preparing 1,3-butadiene using the reactor.
- the method of preparing 1,3-butadiene according to the present invention includes i) filling a reactor with the catalyst for oxidative dehydrogenation as a fixed bed; and ii) performing oxidative dehydrogenation while continuously passing reactants containing a C4 compound including normal butene through the catalyst bed of the reactor filled with the catalyst, wherein the reactor in step i) is a fixed-bed reactor filled with the catalyst for oxidative dehydrogenation in an n-layer structure (n being an integer of 2 or more) in a progressive dilution manner, wherein each stage of the n-stage structure satisfies Equations 1 and 2.
- the method of preparing 1,3-butadiene according to the present invention includes i) filling a reactor with the catalyst for oxidative dehydrogenation as a fixed bed; and ii) performing oxidative dehydrogenation while continuously passing reactants containing a C4 compound including normal butene through the catalyst bed of the reactor filled with the catalyst, wherein the reactor in step i) is a fixed-bed reactor, wherein the catalyst for oxidative dehydrogenation is diluted and the fixed-bed reactor is filled with the diluted catalyst so as to satisfy Equation 6.
- the C4 compound can include, for example, one or more normal butene selected from 2-butene (trans-2-butene, cis-2-butene) and 1-butene, and can optionally further include normal butane or C4 raffinate-3.
- the reactants can further include one or more selected from air, nitrogen, steam, and carbon dioxide, and preferably further includes nitrogen and steam.
- the reactants can include a C4 compound, oxygen, steam, and nitrogen in a molar ratio of 1:0.1 to 1.5:1 to 15:0.5 to 10 or 1:0.5 to 1.2:5 to 12:0.5 to 5.
- the method of preparing butadiene according to the present invention shows excellent reaction efficiency and little generation of wastewater even when steam is used in a small amount (e.g., 1 to 10 mol or 5 to 10 mol based on 1 mol of the C4 compound).
- the method provides the effect of reducing wastewater treatment cost and the effect of reducing energy consumed in the process.
- the oxidative dehydrogenation reaction can be performed at a reaction temperature of 250 to 500° C., 300 to 450° C., 320 to 400° C., 330 to 380° C., or 350 to 370° C. Within this range, reaction efficiency can be excellent without greatly increasing energy cost, thereby increasing the productivity of 1,3-butadiene.
- the ⁇ T value calculated by Equation 7 below can be 105° C. or less, 104° C. or less, 90° C. or less, 80° C. or less, 70° C. or less, 60° C. or less, 50° C. or less, 40° C. or less, 20 to 70° C., or 20 to 45° C.
- ⁇ T(° C.) reaction temperature ⁇ the maximum temperature inside a catalyst bed [Equation 7]
- the maximum temperature inside the catalyst bed means the part of the catalyst bed with the highest temperature during reaction.
- the maximum temperature inside the catalyst bed can be measured, for example, by connecting a thermocouple (TC) to a transfer device and then performing scanning while moving the thermocouple from the top of the reactor to the bottom of the reactor at constant velocity.
- TC thermocouple
- oxidative dehydrogenation can be performed at a gas hourly space velocity (GHSV) of 50 to 2,000 h ⁇ 1 , 50 to 1,500 h ⁇ 1 , or 50 to 1,000 h ⁇ 1 based on normal butene.
- GHSV gas hourly space velocity
- reaction efficiency can be excellent, thereby improving conversion rate, selectivity, and yield.
- the reactor is not particularly limited as long as the reactor includes the catalyst system for oxidative dehydrogenation, but can be, for example, a multi-tube reactor or a plate reactor.
- 2 L of aqueous ammonia adjusted to have a pH of 8 was prepared.
- a metal precursor solution containing 2 L of distilled water, 288.456 g of zinc chloride (ZnCl 2 ), and 1132.219 g of iron chloride (FeCl 3 ) was prepared.
- the prepared metal precursor solution was added dropwise to the prepared aqueous ammonia, and at the same time, 9 wt % aqueous ammonia was added thereto to adjust the pH to 8.
- Alumina balls having a packing density of 0.9 to 1.2 kg/m 3 were added to a rotary chamber under a vacuum atmosphere. Then, the catalyst slurry was coated on the alumina balls having an average particle diameter of 5 mm by spraying the catalyst slurry while rotating the rotary chamber at about 30 to 50 rpm.
- the rotary chamber was set to a temperature of 50 to 80° C.
- a coating catalyst was prepared by drying the catalyst slurry-coated alumina balls in an oven set to 90 to 120° C. so that distilled water was evaporated.
- the coating catalyst having ZnFe 2 O 4 in an amount of 14 wt % was mixed with alumina as a dilution filler as shown in Table 1, and a tubular reactor was filled with the catalyst in a three-layer structure and in a gradual dilution manner. Then, the conversion rate of butene, selectivity for 1,3-butadiene, 1,3-butadiene yield, and selectivity for CO x were measured.
- the C4 compound containing trans-2-butene and cis-2-butene, oxygen, steam, and nitrogen as reactants were mixed in a molar ratio of 1:1:8:1.
- the amount of each of the C4 compound, oxygen, and nitrogen was controlled using a mass flow controller, and the injection rate of steam was controlled using a liquid pump.
- the feed rate of reactants was set so that a gas hourly space velocity (GHSV) was 66 h ⁇ 1 based on normal butene in the C4 compound.
- the reaction was performed at the reaction temperature shown in Table 1 below.
- a reactor was filled with the catalyst composition in a gradual dilution manner in a three-layer structure as shown in Table 2 below. Then, reaction was performed under the same conditions and in the same manner as in Example 1, except that the reaction was performed at the temperature specified in Table 2 below.
- the coating catalyst containing ZnFe 2 O 4 in an amount of 14 wt % was diluted by mixing with a dilution filler as shown in Table 3 and a tubular reactor was filled with the diluted catalyst. Then, reaction was performed under the same conditions and in the same manner as in Example 1, except that reaction temperature was set to 365° C.
- the coating catalyst containing ZnFe 2 O 4 in an amount of 27 wt % was diluted by mixing with a dilution filler as shown in Table 3 and a tubular reactor was filled with the diluted catalyst. Then, reaction was performed under the same conditions and in the same manner as in Example 1, except that reaction temperature was set to 340° C.
- ZnFe 2 O 4 powder prepared in the same manner as in Preparation Examples was kneaded with distilled water and an alcohol and then extrusion-molded to obtain pellets having a diameter of 2 mm and a length of 2 mm, followed by drying at 90° C. for 4 hours to obtain a catalyst in the form of pellets.
- 6 volume % of the prepared catalyst was mixed with 94 volume % of alumina balls, and the mixture was loaded into a reactor. Then, reaction was performed under the same conditions and in the same manner as in Example 1, except that reaction temperature was set to 365° C.
- ZnFe 2 O 4 powder prepared in the same manner as in Preparation Examples was kneaded with distilled water and an alcohol and then extrusion-molded to obtain pellets having a diameter of 2 mm and a length of 2 mm, followed by drying at 90° C. for 4 hours to obtain a catalyst in the form of pellets.
- a reactor was filled with the prepared catalyst in a gradual dilution manner as shown in Table 4. Then, reaction was performed under the same conditions and in the same manner as in Example 1, except that reaction temperature was set to 375° C.
- a tubular reactor was filled with the coating catalyst containing ZnFe 2 O 4 in an amount of 14 wt %. In this case, addition of a dilution filler was omitted. Then, reaction was performed under the same conditions and in the same manner as in Example 3, except that reaction temperature was set to 343° C.
- a tubular reactor was filled with the coating catalyst containing ZnFe 2 O 4 in an amount of 27 wt %. In this case, addition of a dilution filler was omitted. Then, reaction was performed under the same conditions and in the same manner as in Example 4, except that reaction temperature was set to 325° C.
- Example 3 Compared with Example 3, in the case of Comparative Example 3 in which the same concentration of the coating catalyst was used as in Example 3, even though reaction temperature was set to be as low as 22° C., it was confirmed that the maximum temperature inside a catalyst bed was higher by 10° C., and reaction activity was significantly decreased. In the case of Comparative Example 4, although the maximum temperature inside a catalyst bed was the highest, it was confirmed that reaction activity was significantly decreased.
- Reaction was performed under the same conditions and in the same manner as in Example 1, except that, when a coating catalyst was prepared, alumina balls having a packing density of 0.5 kg/m 3 were used.
- Reaction was performed under the same conditions and in the same manner as in Example 1, except that, when a coating catalyst was prepared, alumina balls having a packing density of 2.0 kg/m 3 were used.
- ZnFe 2 O 4 powder prepared in the same manner as in Preparation Examples was kneaded with distilled water and an alcohol and then extrusion-molded to obtain pellets having a diameter of 5 mm and a length of 5 mm, followed by drying at 90° C. for 4 hours to obtain a catalyst in the form of pellets.
- a reactor was filled with the prepared catalyst. In this case, addition of a dilution filler was omitted. Then, reaction was performed under the same conditions and in the same manner as in Example 1, except that reaction temperature was set to 291° C.
- FIG. 1 is a graph showing the temperature distribution of the catalyst bed when oxidative dehydrogenation is performed using the catalyst system according to Example 1
- FIG. 2 is a graph showing the temperature distribution of the catalyst bed when oxidative dehydrogenation is performed using the catalyst system according to Additional Comparative Example 3 (conventional technology).
- the present invention when used, heat generated inside a reactor can be effectively controlled.
- the present invention can provide a reaction system with a stable temperature gradient.
- the catalyst system of the present invention can improve the efficiency of oxidative dehydrogenation.
Abstract
Provided is a catalyst system for oxidative dehydrogenation, a reactor for preparing butadiene including the catalyst system, and a method of preparing 1,3-butadiene. In the catalyst system for oxidative dehydrogenation, a coating catalyst is diluted with a specific dilution filler and a reactor is filled with the diluted catalyst, or a reactor is filled with a catalyst for oxidative dehydrogenation so that the concentration of an active ingredient included in the catalyst gradually increases in the direction from reactants inlet in which reactants are fed into the reactor to products outlet. The catalyst system for oxidative dehydrogenation can efficiently control heat generated inside a reactor, thereby improving conversion rate, selectivity, yield, and long-term stability of a catalyst.
Description
This application is a National Stage Application of International Application No. PCT/KR2018/014736 filed on Nov. 27, 2018, which claims the benefit of Korean Patent Application No. 10-2017-0162431, filed on Nov. 30, 2017, in the Korean Intellectual Property Office, the disclosure of which is incorporated herein in its entirety by reference.
The present invention relates to a catalyst system for oxidative dehydrogenation, a reactor for preparing butadiene including the catalyst system, and a method of preparing 1,3-butadiene. More specifically, the present invention relates to a catalyst system for oxidative dehydrogenation, wherein a coating catalyst having a porous support coated with an active ingredient is diluted with a dilution filler and a reactor is filled with the diluted catalyst, or a reactor is filled with a catalyst for oxidative dehydrogenation so that the concentration of an active ingredient included in the catalyst gradually increases in the direction from reactants inlet in which reactants are fed into the reactor to products outlet. According to the catalyst system of the present invention, heat generated inside a reactor can be efficiently controlled, whereby conversion rate, selectivity, and yield can be greatly improved and long-term stability of a catalyst can be improved.
1,3-butadiene, a major basic product of petroleum fraction, is a representative raw material used in preparation of synthetic rubber, and the price thereof fluctuates rapidly in connection with supply and demand of the petrochemical industry. Examples of methods of preparing 1,3-butadiene include naphtha cracking, direct dehydrogenation of normal butene, oxidative dehydrogenation of normal butene, and the like.
According to the method of preparing 1,3-butadiene by oxidative dehydrogenation of normal butene, butene and oxygen react in the presence of a metal oxide catalyst to generate 1,3-butadiene and water. In this case, water generated as a result of the reaction is stable. Thus, the method is thermodynamically very advantageous. In addition, since oxidative dehydrogenation of normal butene is an exothermic reaction unlike direct dehydrogenation, reaction can be performed at a low temperature. Thus, 1,3-butadiene can be obtained in high yield while reducing energy consumption. In addition, in the case of oxidative dehydrogenation, since an oxidizing agent is added, the generation amount of carbon deposits which shorten catalyst life by poisoning the catalyst is reduced. Further, since removal of the oxidizing agent is easy, the method of preparing 1,3-butadiene using oxidative dehydrogenation is very suitable for commercialization.
However, heat generated during oxidative dehydrogenation is accumulated in a catalyst bed, deteriorating a catalyst, thereby degrading catalyst life, and side reaction is promoted by excess heat, thereby reducing reaction efficiency. As a result, butadiene yield, selectivity for butadiene, and the conversion rate of butene can be lowered.
To solve these problems, a method of controlling space velocity by controlling the amount of gas fed to a reactor has been proposed. However, this method was unsatisfactory in terms of productivity and yield. Thus, development of a system for oxidative dehydrogenation of butene that can effectively control heat generated inside a reactor while having high productivity is still required.
[Patent Document] (Patent Document 1) KR 10-1508776 B1
Therefore, the present invention has been made in view of the above problems, and it is one object of the present invention to provide a catalyst system for oxidative dehydrogenation capable of effectively controlling heat generated inside a reactor to prevent catalyst deterioration, thereby improving conversion rate, selectivity, and yield.
It is another object of the present invention to provide a reactor for preparing butadiene including the catalyst system for oxidative dehydrogenation and a method of preparing 1,3-butadiene using the reactor.
The above and other objects can be accomplished by the present invention described below.
In accordance with one aspect of the present invention, provided is a catalyst system for oxidative dehydrogenation, wherein a reactor is filled with a catalyst for oxidative dehydrogenation in an n-layer structure (n being an integer of 2 or more), wherein the catalyst is diluted and the reactor is filled with the diluted catalyst so that each layer of the n-layer structure satisfies Equations 1 and 2 below.
X wt %+Y wt %+Z wt %=100 wt %, [Equation 1]
X wt %+Y wt %+Z wt %=100 wt %, [Equation 1]
wherein X represents a content of AB2O4 and is 3 to 30, wherein A is one or more selected from the group consisting of copper (Cu), radium (Ra), barium (Ba), strontium (Sr), calcium (Ca), beryllium (Be), zinc (Zn), magnesium (Mg), manganese (Mn), cerium (Ce), zirconium (Zr), lanthanum (La), and cobalt (Co) and B is iron (Fe); Y is a content of a porous support and is 20 to 97; and Z is a content of one or more dilution fillers selected from alumina, silica, silicon carbide, zirconia, titania, and cordierite and is 0 to 77.
X n >X n−1, [Equation 2]
X n >X n−1, [Equation 2]
wherein, with respect to the direction in which reactants are fed into the reactor, Xn represents X for the n-th layer, and Xn−1 represents X for the (n−1)th layer.
In accordance with another aspect of the present invention, provided is a catalyst system for oxidative dehydrogenation, wherein a reactor is filled with a catalyst for oxidative dehydrogenation, wherein the catalyst is diluted and the reactor is filled with the diluted catalyst so as to satisfy Equation 6 below.
X wt %+Y wt %+Z wt %=100 wt %, [Equation 6]
X wt %+Y wt %+Z wt %=100 wt %, [Equation 6]
wherein X is a content of AB2O4 and is 5 to 25, wherein A is one or more selected from the group consisting of copper (Cu), radium (Ra), barium (Ba), strontium (Sr), calcium (Ca), beryllium (Be), zinc (Zn), magnesium (Mg), manganese (Mn), cerium (Ce), zirconium (Zr), lanthanum (La), and cobalt (Co) and B is iron (Fe); Y is a content of a porous support and is 25 to 85; and Z is a content of one or more selected from alumina, silica, silicon carbide, zirconia, titania, and cordierite and is 10 to 70.
In accordance with another aspect of the present invention, provided is a reactor for preparing butadiene including the catalyst system for oxidative dehydrogenation.
In accordance with yet another aspect of the present invention, provided is a method of preparing 1,3-butadiene including performing oxidative dehydrogenation using the reactor for preparing butadiene of the present invention, wherein the oxidative dehydrogenation is performed while continuously passing reactants containing a C4 compound including normal butene through the catalyst bed of the reactor.
As apparent from the foregoing, the present invention advantageously provides a catalyst system for oxidative dehydrogenation, wherein a catalyst having a porous support on which an active ingredient is uniformly and firmly coated is diluted in a dilution filler and a reactor is filled with the diluted catalyst, or a reactor is filled with a catalyst for oxidative dehydrogenation so that the concentration of an active ingredient included in the catalyst gradually increases in the direction from reactants inlet in which reactants are fed into the reactor to products outlet. When the catalyst system according to the present invention is used, it is possible to effectively control distribution of heat generated inside a reactor during oxidative dehydrogenation without adding a separate apparatus or changing the conventional manufacturing facilities, and thus to improve conversion rate, selectivity, and yield. In addition, catalyst deterioration can be reduced, thereby improving long-term stability of a catalyst.
Hereinafter, the catalyst system for oxidative dehydrogenation according to the present invention will be described in detail.
In the catalyst system for oxidative dehydrogenation according to the present invention, a catalyst for oxidative dehydrogenation is diluted to satisfy Equation 1 below, and a reactor is filled with the diluted catalyst.
X wt %+Y wt %+Z wt %=100 wt %, [Equation 1]
X wt %+Y wt %+Z wt %=100 wt %, [Equation 1]
wherein X represents a content of AB2O4 and is 3 to 30, wherein A is one or more selected from the group consisting of copper (Cu), radium (Ra), barium (Ba), strontium (Sr), calcium (Ca), beryllium (Be), zinc (Zn), magnesium (Mg), manganese (Mn), cerium (Ce), zirconium (Zr), lanthanum (La), and cobalt (Co) and B is iron (Fe); Y is a content of a porous support and is 20 to 97; and Z is a content of one or more dilution fillers selected from alumina, silica, silicon carbide, zirconia, titania, and cordierite and is 0 to 77.
X n >X n−1, [Equation 2]
X n >X n−1, [Equation 2]
wherein, with respect to the direction in which reactants are fed into the reactor, Xn represents X for the n-th layer, and Xn−1 represents X for the (n−1)th layer.
According to the present invention, AB2O4 is the active ingredient of a catalyst, and the catalyst for oxidative dehydrogenation is a coating catalyst having a porous support coated with the active ingredient AB2O4.
For example, AB2O4 can be a zinc ferrite (ZnFe2O4), wherein A is zinc (Zn) and B is iron (Fe). In this case, the catalyst can exhibit excellent activity in oxidative dehydrogenation of normal butene, and can have high selectivity for 1,3-butadiene.
For example, AB2O4 can have an average particle diameter of 0.1 to 250 μm, 10 to 200 μm, 15 to 150 μm, 15 to 100 μm, 15 to 60 μm, or 25 to 60 μm. Within this range, coating of the active ingredient on the porous support can be easily performed, and the catalyst can have excellent activity, thereby improving reaction efficiency.
According to the present invention, AB2O4 having an average particle diameter within the above range can be selected, for example, using a sieving method.
For example, in Equation 1, X is preferably 3 to 30, 3 to 27, 3.5 to 20, 3.5 to 18, or 3.5 to 14. Within this range, reaction efficiency can be excellent, thereby improving yield, selectivity, and conversion rate.
For example, the porous support can have an average particle diameter of 3 to 7 mm or 4 to 6 mm. Within this range, reaction efficiency can be excellent, thereby improving conversion rate and selectivity.
For example, the porous support can have an average pore size of 50 to 200 μm or 100 to 150 μm. Within this range, coating of AB2O4 powder can be easy performed and desorption of the powder can be prevented.
According to the present invention, the average particle diameter and average pore size of the porous support can be measured, for example, using a method of calculating a surface area and an average pore size through adsorption isotherm of nitrogen by the BET method and the BJH (Barret-Joyner-Halenda) method, respectively, or using a mercury impregnation method.
The porous support can have a packing density of 0.8 to 1.5 kg/m3 or 0.9 to 1.3 kg/m3. Coating rate is determined based on the packing density. When the porous support has a packing density within this range, separation or desorption of the AB2O4 powder can be prevented, and the support can be easily coated with the powder. Further, when oxidative dehydrogenation is performed, the conversion rate of butene or 1,3-butadiene yield can be increased, and excessive increase in the temperature inside a catalyst bed can be suppressed, thereby increasing thermal stability.
According to the present invention, packing density is calculated by dividing mass capable of filling a tubular measuring cylinder to 100 cc by a volume value of 100 cc thereof.
The porous support is preferably spherical, hollow, or in the form of pellets. In this case, reaction efficiency can be excellent, thereby improving yield, selectivity, and conversion rate.
In the present invention, spherical, pellet, and hollow shapes are not particularly limited as long as they are within the ordinary range of those skilled in the art of porous support technology, and these shapes are clearly distinguished.
For example, the porous support can be one or more selected from the group consisting of alumina, silica, titania, zirconia, silicon carbide, and cordierite, and is preferably alumina or silica. In this case, mechanical strength for filling a reactor is satisfied and side reaction can be reduced.
More preferably, the porous support is alumina. In this case, mechanical strength can be ensured, and butadiene yield and selectivity can be prevented from being lowered by side reaction during oxidative dehydrogenation.
For example, in Equation 1, Y can be 20 to 97, 21 to 90, 21 to 86, 30 to 86, or 40 to 86. Within this range, catalytic activity and heat generation control can be excellent.
The coating catalyst of the present invention can further include an organic/inorganic binder when necessary. In this case, the binder can be included in an amount of 30 parts by weight or less, 0.1 to 20 parts by weight, or 0.1 to 10 parts by weight based on 100 parts by weight of AB2O4. Within this range, the abrasion resistance of the catalyst can be improved without significantly lowering the efficiency of oxidative dehydrogenation.
For example, the binder can include aluminum-silicate, methylcellulose, hydroxypropyl methylcellulose, or both. When the binder is contained in an appropriate amount, the abrasion resistance of the catalyst can be improved without significantly lowering the efficiency of oxidative dehydrogenation.
As another example, the coating catalyst of the present invention can be a binder-free catalyst. In this case, since side reaction is not caused by the binder, the conversion rate of normal butene and selectivity for butadiene can be greatly increased. In addition, since introduction of some components is omitted, a process of preparing the catalyst can be simplified, thereby reducing process costs.
According to the present invention, binder-free means that an organic or inorganic binder is omitted when preparing a catalyst and/or that a catalyst is prepared without the binder.
For example, a fixed-bed reactor can be filled with the catalyst for oxidative dehydrogenation according to the present invention in a 2- to 8-layer, 3- to 8-layer, 3- to 6-layer, or 3- to 5-layer structure. Within this range, distribution of heat generated inside the reactor can be effectively controlled without significantly increasing process costs. Thus, when butadiene is prepared, conversion rate, selectivity, and yield can be greatly improved, and long-term stability of the catalyst can be improved.
For example, the catalyst system of the present invention satisfies Equation 3 below. In this case, excessive heat generation in the catalyst bed can be effectively prevented during reaction. As a result, when butadiene is prepared, conversion rate, selectivity, yield, and long-term stability of the catalyst can be improved.
(X n −X n−1)≥2, [Equation 3]
(X n −X n−1)≥2, [Equation 3]
wherein Xn represents X for the n-th layer, and Xn−1 represents X for the (n−1)th layer.
According to the present invention, at least one of the n layers can have a Z value greater than 0. When the coating catalyst is mixed with a dilution filler and a reactor is filled with the coating catalyst so that the concentration of the catalyst is gradually decreased, heat generation control can be effectively performed during reaction, thereby improving reaction efficiency.
According to the present invention, the dilution filler can be, for example, one or more selected from alumina, silica, silicon carbide, zirconia, titania, and cordierite, and is preferably one or more selected from alumina and silica. In this case, it is possible to suppress generation of excessive reaction heat while minimizing side reaction, thereby greatly improving the efficiency of oxidative dehydrogenation.
The catalyst system of the present invention satisfies Equation 4 below when at least one layer has a Z value other than 0. In this case, excessive temperature increase of the catalyst bed due to excessive heat may be suppressed, and thus productivity such as conversion rate, selectivity, and yield can be greatly improved when butadiene is prepared.
(Yn−Yn−1)≥15, [Equation 4]
(Yn−Yn−1)≥15, [Equation 4]
wherein Yn represents Y for the n-th layer, and Yn−1 represents Y for the (n−1)th layer.
In addition, the catalyst system of the present invention satisfies Equation 5 below. In this case, heat generation due to oxidative dehydrogenation can be effectively controlled so that the activity or stability of the catalyst can be continuously maintained high and reaction efficiency can be improved.
(Z n−1 −Z n)≥20, [Equation 5]
(Z n−1 −Z n)≥20, [Equation 5]
wherein Zn represents Z for the n-th layer, and Zn−1 represents Z for the (n−1)th layer.
As another example, in the catalyst system for oxidative dehydrogenation according to the present invention, a reactor is filled with the catalyst for oxidative dehydrogenation in an n-layer structure (n being an integer of 2 or more). In this case, the catalyst is diluted and the reactor is filled with the diluted catalyst so that each layer satisfies Equations 1 and 2. In addition, the porous support has a packing density of 0.8 to 1.5 kg/m3 or 0.9 to 1.2 kg/m3. In this case, separation or peeling of AB2O4 powder from the porous support can be prevented, and the support can be uniformly and firmly coated with the catalyst. In addition, heat generation inside the catalyst bed during oxidative dehydrogenation can be effectively controlled, and side reaction can be suppressed, thereby improving the conversion rate of butene, butadiene yield, and selectivity.
As a specific example, in the catalyst system for oxidative dehydrogenation according to the present invention, a reactor is filled with the catalyst for oxidative dehydrogenation in a three-layer structure. In this case, the catalyst is diluted and the reactor is filled with the diluted catalyst so that each layer satisfies Equations 1 and 2 below. With respect to the direction in which reactants are fed into the reactor, in the case of the first layer, X is 3.5 to 7; Y is 21.5 to 43; and Z is 50 to 75, in the case of the second layer, X is 7 to 10.5; Y is 43 to 64.5; and Z is 25 to 50, and in the case of the third layer, X is 13 to 18; Y is 82 to 87; and Z is 0 to 5. In this case, excessive temperature rise inside the catalyst bed can be effectively suppressed. Consequently, compared to the conventional catalyst system, the conversion rate of butene and selectivity for 1,3-butadiene can be improved.
X wt %+Y wt %+Z wt %=100 wt %, [Equation 1]
X wt %+Y wt %+Z wt %=100 wt %, [Equation 1]
wherein X is a content of zinc ferrite powder wherein A is Zn and B is Fe, Y is a content of a porous support, and Z is a content of one or more dilution fillers selected from alumina, silica, silicon carbide, and zirconia, wherein the porous support is alumina having a packing density of 0.8 to 1.5 kg/m3.
X n >X n−1, [Equation 2]
X n >X n−1, [Equation 2]
wherein, with respect to the direction in which reactants are fed into the reactor, Xn represents X for the n-th layer, and Xn−1 represents X for the (n−1)th layer, wherein n is the total number of layers and is 3.
As a preferred example, in the first layer, X is 3 to 4.5; Y is 20 to 35; and Z is 60.5 to 77, in the second layer, X is 5 to 8; Y is 40 to 50; and Z is 45 to 55, and in the third layer, X is 10 to 16; Y is 60 to 90; and Z is 0 to 30. In this case, excessive temperature rise inside the catalyst bed can be effectively suppressed. When oxidative dehydrogenation is performed using the catalyst system, side reaction can be suppressed, and the conversion rate of butene, selectivity for butadiene, and yield can be improved.
In addition, as another example, in the catalyst system of the present invention, the catalyst for oxidative dehydrogenation is diluted and a reactor is filled with the catalyst so as to satisfy Equation 6 below.
X wt %+Y wt %+Z wt %=100 wt %, [Equation 6]
X wt %+Y wt %+Z wt %=100 wt %, [Equation 6]
wherein X is a content of AB2O4 and is 5 to 25, wherein A is one or more selected from the group consisting of copper (Cu), radium (Ra), barium (Ba), strontium (Sr), calcium (Ca), beryllium (Be), zinc (Zn), magnesium (Mg), manganese (Mn), cerium (Ce), zirconium (Zr), lanthanum (La), and cobalt (Co) and B is iron (Fe); Y is a content of a porous support and is 25 to 85; and Z is a content of one or more dilution fillers selected from alumina, silica, silicon carbide, zirconia, titania, and cordierite and is 10 to 70.
Hereinafter, a catalyst system for oxidative dehydrogenation according to another embodiment of the present invention, wherein the catalyst is diluted and a reactor for oxidative dehydrogenation is filled with the diluted catalyst so as to satisfy Equation 6, will be described. In explaining the system, the overlapping description with the incremental dilution filling system of the above-mentioned catalyst for oxidative dehydrogenation will be omitted.
In Equation 6, X is preferably 5 to 25, 7 to 20, 7 to 18, 7 to 14, 7 to 13.5, or 7 to 11. Within this range, reaction efficiency can be excellent, thereby improving yield, selectivity, and conversion rate.
In Equation 6, Y can be, for example, 25 to 85, 35 to 80, 36 to 75, 36.5 to 70, 36.5 to 60, or 40 to 50. Within this range, catalytic activity and catalyst stability can be maintained high, and the productivity of butadiene can be increased.
In Equation 6, Z can be, for example, 10 to 70, 20 to 70, or 40 to 60. Within this range, excessive heat generation due to oxidative dehydrogenation can be effectively suppressed, thereby improving catalyst stability and reaction efficiency.
As a preferred example, the porous support can have a packing density of 0.8 to 1.5 kg/m3 or 0.9 to 1.2 kg/m3. Within this range, the mechanical strength of the coating catalyst can be excellent, and separation or peeling of AB2O4 powder from the porous support can be prevented. In addition, heat generation in the catalyst bed during oxidative dehydrogenation can be effectively suppressed, and butadiene yield and selectivity for butadiene can be improved.
The catalyst system can be an oxidative-dehydrogenation catalyst system for preparation of 1,3-butadiene.
In addition, the present invention provides a reactor for preparing butadiene including the catalyst system and a method of preparing 1,3-butadiene using the reactor.
For example, the method of preparing 1,3-butadiene according to the present invention includes i) filling a reactor with the catalyst for oxidative dehydrogenation as a fixed bed; and ii) performing oxidative dehydrogenation while continuously passing reactants containing a C4 compound including normal butene through the catalyst bed of the reactor filled with the catalyst, wherein the reactor in step i) is a fixed-bed reactor filled with the catalyst for oxidative dehydrogenation in an n-layer structure (n being an integer of 2 or more) in a progressive dilution manner, wherein each stage of the n-stage structure satisfies Equations 1 and 2.
As another example, the method of preparing 1,3-butadiene according to the present invention includes i) filling a reactor with the catalyst for oxidative dehydrogenation as a fixed bed; and ii) performing oxidative dehydrogenation while continuously passing reactants containing a C4 compound including normal butene through the catalyst bed of the reactor filled with the catalyst, wherein the reactor in step i) is a fixed-bed reactor, wherein the catalyst for oxidative dehydrogenation is diluted and the fixed-bed reactor is filled with the diluted catalyst so as to satisfy Equation 6.
When a specific catalyst is diluted and a reactor is filled with the diluted catalyst, or a reactor is filled with a specific catalyst in a progressive dilution manner, and then oxidative dehydrogenation is performed, heat generation inside the reactor can be effectively controlled. In particular, when a fixed-bed reactor is filled with a specific catalyst for oxidative dehydrogenation in a progressive dilution manner, heat generation control effect can be maximized, allowing catalytic activity and catalyst stability to remain high over a long period of time. In addition, the conversion rate of butene, selectivity for butadiene, and yield can be greatly improved.
The C4 compound can include, for example, one or more normal butene selected from 2-butene (trans-2-butene, cis-2-butene) and 1-butene, and can optionally further include normal butane or C4 raffinate-3.
For example, the reactants can further include one or more selected from air, nitrogen, steam, and carbon dioxide, and preferably further includes nitrogen and steam.
As a specific example, the reactants can include a C4 compound, oxygen, steam, and nitrogen in a molar ratio of 1:0.1 to 1.5:1 to 15:0.5 to 10 or 1:0.5 to 1.2:5 to 12:0.5 to 5. In addition, the method of preparing butadiene according to the present invention shows excellent reaction efficiency and little generation of wastewater even when steam is used in a small amount (e.g., 1 to 10 mol or 5 to 10 mol based on 1 mol of the C4 compound). Ultimately, the method provides the effect of reducing wastewater treatment cost and the effect of reducing energy consumed in the process.
For example, the oxidative dehydrogenation reaction can be performed at a reaction temperature of 250 to 500° C., 300 to 450° C., 320 to 400° C., 330 to 380° C., or 350 to 370° C. Within this range, reaction efficiency can be excellent without greatly increasing energy cost, thereby increasing the productivity of 1,3-butadiene.
In addition, in oxidative dehydrogenation, the ΔT value calculated by Equation 7 below can be 105° C. or less, 104° C. or less, 90° C. or less, 80° C. or less, 70° C. or less, 60° C. or less, 50° C. or less, 40° C. or less, 20 to 70° C., or 20 to 45° C.
ΔT(° C.)=reaction temperature−the maximum temperature inside a catalyst bed [Equation 7]
ΔT(° C.)=reaction temperature−the maximum temperature inside a catalyst bed [Equation 7]
According to the present invention, the maximum temperature inside the catalyst bed means the part of the catalyst bed with the highest temperature during reaction.
In addition, the maximum temperature inside the catalyst bed can be measured, for example, by connecting a thermocouple (TC) to a transfer device and then performing scanning while moving the thermocouple from the top of the reactor to the bottom of the reactor at constant velocity.
For example, oxidative dehydrogenation can be performed at a gas hourly space velocity (GHSV) of 50 to 2,000 h−1, 50 to 1,500 h−1, or 50 to 1,000 h−1 based on normal butene. Within this range, reaction efficiency can be excellent, thereby improving conversion rate, selectivity, and yield.
In the present invention, the reactor is not particularly limited as long as the reactor includes the catalyst system for oxidative dehydrogenation, but can be, for example, a multi-tube reactor or a plate reactor.
Hereinafter, the present invention will be described in more detail with reference to the following preferred examples. However, these examples are provided for illustrative purposes only and should not be construed as limiting the scope and spirit of the present invention. In addition, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention, and such changes and modifications are also within the scope of the appended claims.
1. Preparation of ZnFe2O4 Powder
2 L of aqueous ammonia adjusted to have a pH of 8 was prepared. In a separate container, a metal precursor solution containing 2 L of distilled water, 288.456 g of zinc chloride (ZnCl2), and 1132.219 g of iron chloride (FeCl3) was prepared. The prepared metal precursor solution was added dropwise to the prepared aqueous ammonia, and at the same time, 9 wt % aqueous ammonia was added thereto to adjust the pH to 8. To obtain a sample having a uniform composition, all of the metal precursor solution was added dropwise with stirring for 1 hour using an agitator, aged for 1 hour, and then the solution including precipitate was washed with 4 L of distilled water and the precipitate was separated by filtration. The separated precipitate was dried for 16 hours, and then burned at 650° C. to obtain ZnFe2O4 powder. The obtained powder was pulverized, and then powder having a size of 45 μm or less was selected using a sieving method.
2. Preparation of Coating Catalyst
ZnFe2O4 powder quantified so that ZnFe2O4 has a ratio of 14 wt % or 27 wt % based on 100 wt % in total of ZnFe2O4 and alumina balls was dispersed in distilled water to prepare a catalyst slurry having a concentration of 10 to 30 wt %. Alumina balls having a packing density of 0.9 to 1.2 kg/m3 were added to a rotary chamber under a vacuum atmosphere. Then, the catalyst slurry was coated on the alumina balls having an average particle diameter of 5 mm by spraying the catalyst slurry while rotating the rotary chamber at about 30 to 50 rpm. When coating was performed, the rotary chamber was set to a temperature of 50 to 80° C. After the coating process was completed, a coating catalyst was prepared by drying the catalyst slurry-coated alumina balls in an oven set to 90 to 120° C. so that distilled water was evaporated.
The coating catalyst having ZnFe2O4 in an amount of 14 wt % was mixed with alumina as a dilution filler as shown in Table 1, and a tubular reactor was filled with the catalyst in a three-layer structure and in a gradual dilution manner. Then, the conversion rate of butene, selectivity for 1,3-butadiene, 1,3-butadiene yield, and selectivity for COx were measured.
The C4 compound containing trans-2-butene and cis-2-butene, oxygen, steam, and nitrogen as reactants were mixed in a molar ratio of 1:1:8:1. At this time, the amount of each of the C4 compound, oxygen, and nitrogen was controlled using a mass flow controller, and the injection rate of steam was controlled using a liquid pump. The feed rate of reactants was set so that a gas hourly space velocity (GHSV) was 66 h−1 based on normal butene in the C4 compound. The reaction was performed at the reaction temperature shown in Table 1 below.
| TABLE 1 | ||
| GHSV/mole ratio of butene:oxygen:steam:nitrogen = | ||
| 66 h−1/1:1:8:1, 355° C. | ||
| X [content of | Y [content of | Z [content of | |
| ZnFe2O4, | porous support, | dilution filler, | |
| Classification | wt %] | wt % ] | wt % ] |
| Third layer | 14 | 86 | 0 |
| Second layer | 10.5 | 64.5 | 25 |
| First layer | 7 | 43 | 50 |
| * In table 1, each of X, Y, and Z is based on 100 wt % of the total amount thereof. | |||
A reactor was filled with the catalyst composition in a gradual dilution manner in a three-layer structure as shown in Table 2 below. Then, reaction was performed under the same conditions and in the same manner as in Example 1, except that the reaction was performed at the temperature specified in Table 2 below.
| TABLE 2 | ||
| GHSV/mole ratio of butene:oxygen:steam:nitrogen = | ||
| 66 h−1/1:1:8:1, 360° C. | ||
| X [content of | Y [content of | Z [content of | |
| ZnFe2O4, | porous support, | dilution filler, | |
| Classification | wt %] | wt % ] | wt % ] |
| Third layer | 14 | 86 | 0 |
| Second layer | 7 | 43 | 50 |
| First layer | 3.5 | 21.5 | 75 |
| * In Table 2, each of X, Y, and Z is based on 100 wt % of the total amount thereof. | |||
The coating catalyst containing ZnFe2O4 in an amount of 14 wt % was diluted by mixing with a dilution filler as shown in Table 3 and a tubular reactor was filled with the diluted catalyst. Then, reaction was performed under the same conditions and in the same manner as in Example 1, except that reaction temperature was set to 365° C.
The coating catalyst containing ZnFe2O4 in an amount of 27 wt % was diluted by mixing with a dilution filler as shown in Table 3 and a tubular reactor was filled with the diluted catalyst. Then, reaction was performed under the same conditions and in the same manner as in Example 1, except that reaction temperature was set to 340° C.
| TABLE 3 | ||
| GHSV/mole ratio of | ||
| butene:oxygen:steam:nitrogen = | ||
| 66 h−1/1:1:8:1 | ||
| X [content | Y [content | Z [content | ||
| Reaction | of | of porous | of dilution | |
| temperature | ZnFe2O4, | support, | filler, | |
| Classification | ( ° C.) | wt % ] | wt % ] | wt % ] |
| Example 3 | 365 | 7 | 43 | 50 |
| Example 4 | 340 | 13.5 | 36.5 | 50 |
| * In Table 3, each of X, Y, and Z is based on 100 wt % of the total amount thereof. | ||||
ZnFe2O4 powder prepared in the same manner as in Preparation Examples was kneaded with distilled water and an alcohol and then extrusion-molded to obtain pellets having a diameter of 2 mm and a length of 2 mm, followed by drying at 90° C. for 4 hours to obtain a catalyst in the form of pellets. 6 volume % of the prepared catalyst was mixed with 94 volume % of alumina balls, and the mixture was loaded into a reactor. Then, reaction was performed under the same conditions and in the same manner as in Example 1, except that reaction temperature was set to 365° C.
ZnFe2O4 powder prepared in the same manner as in Preparation Examples was kneaded with distilled water and an alcohol and then extrusion-molded to obtain pellets having a diameter of 2 mm and a length of 2 mm, followed by drying at 90° C. for 4 hours to obtain a catalyst in the form of pellets. A reactor was filled with the prepared catalyst in a gradual dilution manner as shown in Table 4. Then, reaction was performed under the same conditions and in the same manner as in Example 1, except that reaction temperature was set to 375° C.
| TABLE 4 | ||
| GHSV/mole ratio of butene:oxygen:steam:nitrogen = | ||
| 66h−1/1:1:8:1, 365° C. | ||
| X [content of | Y [content of | Z [content of | |
| ZnFe2O4, | porous support, | dilution filler, | |
| Classification | wt %] | wt % ] | wt % ] |
| Third layer | 9 | — | 91 |
| Second layer | 6 | — | 94 |
| First layer | 3 | — | 97 |
| * In Table 4, each of X and Z is based on 100 wt % of the total amount thereof. | |||
A tubular reactor was filled with the coating catalyst containing ZnFe2O4 in an amount of 14 wt %. In this case, addition of a dilution filler was omitted. Then, reaction was performed under the same conditions and in the same manner as in Example 3, except that reaction temperature was set to 343° C.
A tubular reactor was filled with the coating catalyst containing ZnFe2O4 in an amount of 27 wt %. In this case, addition of a dilution filler was omitted. Then, reaction was performed under the same conditions and in the same manner as in Example 4, except that reaction temperature was set to 325° C.
The products according to Examples and Comparative Examples were analyzed using gas chromatography. The conversion rate of butene, selectivity for 1,3-butadiene, 1,3-butadiene yield, selectivity for COx were calculated according to Equations 8, 9, and 10 below, respectively. The results are shown in Tables 5 and 6.
In addition, when oxidative dehydrogenation was performed using the catalyst systems according to Examples and Comparative Examples, the maximum temperature inside a catalyst bed was analyzed while moving a thermocouple in a thermo-well at the center of a reactor from the inlet of the reactor to the outlet of the reactor at a constant velocity of 4 mm per second.
Conversion rate (%)=[(Number of moles of butene reacted)/(Number of moles of butene supplied)]×100 [Equation 8]
Selectivity (%)=[(Number of moles of 1,3-butadiene or COx generated)/(Number of moles of butene reacted)]×100 [Equation 9]
Yield (%)=[(Number of moles of 1,3-butadiene generated)/(Number of moles of butene supplied)]×100 [Equation 10]
Conversion rate (%)=[(Number of moles of butene reacted)/(Number of moles of butene supplied)]×100 [Equation 8]
Selectivity (%)=[(Number of moles of 1,3-butadiene or COx generated)/(Number of moles of butene reacted)]×100 [Equation 9]
Yield (%)=[(Number of moles of 1,3-butadiene generated)/(Number of moles of butene supplied)]×100 [Equation 10]
| TABLE 5 | |||||||
| Conversion | Selectivity for | Yield of 1.3- | Hot | ||||
| rate of | 1.3-butadiene | butadiene | Selectivity for | spot | ΔT | ||
| butene (%) | (%) | yield (%) | COx (%) | (° C.) | (° C.) | ||
| Example 1 | 89.8 | 88.8 | 79.7 | 9.8 | 400 | 65 |
| Example 2 | 91.2 | 91.7 | 83.6 | 7.1 | 397 | 37 |
| Comparative | 79.6 | 89.3 | 71.1 | 9.1 | 400 | 35 |
| Example 1 | ||||||
| Comparative | 83.9 | 88.4 | 74.2 | 10.2 | 415 | 40 |
| Example 2 | ||||||
| ΔT (° C.): Difference between the maximum temperature inside a catalyst bed and the reaction temperature set during reaction | ||||||
As shown in Table 5, compared with Comparative Examples 1 and 2, in the case of Examples 1 and 2 using the catalyst system according to the present invention, although oxidative dehydrogenation was performed at a relatively low reaction temperature, it was confirmed that the conversion rate of butene, selectivity for 1,3-butadiene, and 1,3-butadiene yield were excellent. In particular, when the catalyst system according to Example 2 was used, the efficiency and activity of oxidative dehydrogenation were excellent. In addition, considering that the difference between the maximum temperature inside a catalyst bed and the reaction temperature was small, it was confirmed that heat generated inside a reactor was effectively controlled.
On the other hand, in the case of the catalyst system according to Comparative Example 1, wherein the catalyst in the form of pellets prepared using ZnFe2O4 powder was diluted by mixing a dilution filler and a reactor was filled with the diluted catalyst, although reaction was performed at a relatively high reaction temperature, it was confirmed that reaction activity was significantly lower than in the cases of Examples. In addition, in the case of Comparative Example 2, although the catalyst in the form of pellets prepared using ZnFe2O4 powder was diluted by mixing with a dilution filler and a reactor was filled with the diluted catalyst in a gradual dilution manner, it was confirmed that reaction activity was lower than in Examples.
From the above results, it can be seen that, when the catalyst system, in which a catalyst having a porous support on which ZnFe2O4 is coated in a predetermined ratio is diluted with a dilution filler and a reactor is filled with the diluted catalyst in a gradual dilution manner, is used to perform oxidative dehydrogenation, the activity of oxidative dehydrogenation is greatly improved. In addition, it can be judged that this is because heat generation inside the reactor is controlled by the novel catalyst system according to the present invention, thereby providing a reaction system with a stable temperature gradient. In addition, from the results of Examples 1 and 2, it can be seen that, when the reactor is filled with the coating catalyst in a gradual dilution manner, dilution ratio affects reaction activity.
| TABLE 6 | |||||||
| Conversion | Selectivity for | Yield of 1.3- | Hot | ||||
| rate of | 1.3-butadiene | butadiene | Selectivity for | spot | ΔT | ||
| butene (%) | (%) | (%) | COx (%) | (° C.) | (° C.) | ||
| Example 3 | 90.4 | 89.0 | 80.5 | 9.8 | 453 | 88 |
| Comparative | 88.3 | 88.5 | 78.1 | 10.1 | 443 | 100 |
| Example 3 | ||||||
| Example 4 | 86.1 | 85.8 | 73.9 | 11.3 | 444 | 104 |
| Comparative | 82.7 | 86.6 | 71.6 | 12.0 | 471 | 146 |
| Example 4 | ||||||
| ΔT (° C.): Difference between the maximum temperature inside a catalyst bed and the reaction temperature set during reaction | ||||||
As shown in Table 6, in the case of the catalyst systems (Examples 3 and 4) in which the coating catalyst is homogeneously diluted with a dilution filler, compared with the systems of Comparative Examples 3 and 4 in which the same coating catalyst was used, but the coating catalyst was not diluted, it was confirmed that the conversion rate of butene, selectivity for 1,3-butadiene, and 1,3-butadiene yield were excellent, and selectivity for COx as a side reaction product and the maximum temperature inside a catalyst bed were significantly decreased. In addition, it was confirmed that this improvement effect was even better when a coating catalyst having a coating ratio of 14 wt % was used.
On the other hand, compared with Example 3, in the case of Comparative Example 3 in which the same concentration of the coating catalyst was used as in Example 3, even though reaction temperature was set to be as low as 22° C., it was confirmed that the maximum temperature inside a catalyst bed was higher by 10° C., and reaction activity was significantly decreased. In the case of Comparative Example 4, although the maximum temperature inside a catalyst bed was the highest, it was confirmed that reaction activity was significantly decreased.
Reaction was performed under the same conditions and in the same manner as in Example 1, except that silicon carbide was used as a dilution filler.
Reaction was performed under the same conditions and in the same manner as in Example 1, except that zirconia was used as a dilution filler.
Reaction was performed under the same conditions and in the same manner as in Example 1, except that, when a coating catalyst was prepared, alumina balls having a packing density of 0.5 kg/m3 were used.
Reaction was performed under the same conditions and in the same manner as in Example 1, except that, when a coating catalyst was prepared, alumina balls having a packing density of 2.0 kg/m3 were used.
ZnFe2O4 powder prepared in the same manner as in Preparation Examples was kneaded with distilled water and an alcohol and then extrusion-molded to obtain pellets having a diameter of 5 mm and a length of 5 mm, followed by drying at 90° C. for 4 hours to obtain a catalyst in the form of pellets. A reactor was filled with the prepared catalyst. In this case, addition of a dilution filler was omitted. Then, reaction was performed under the same conditions and in the same manner as in Example 1, except that reaction temperature was set to 291° C.
The products prepared according to the Additional Examples and Additional Comparative Examples were analyzed in the same manner as described above, and the results are shown in Table 7.
| TABLE 7 | |||||||
| Maximum | |||||||
| Selectivity | Yield of | temperature | |||||
| Conversion | for 1.3- | 1.3- | inside | ||||
| rate of | butadiene | butadiene | Selectivity | catalyst bed | ΔT | ||
| butene (%) | (%) | (%) | for COx (%) | (° C.) | (° C.) | ||
| Additional | 89.2 | 87.4 | 78.0 | 10.5 | 401 | 46 |
| Example 1 | ||||||
| Additional | 86.7 | 87.5 | 75.9 | 11.1 | 407 | 52 |
| Example 2 | ||||||
| Additional | 57.2 | 91.5 | 52.3 | 6.9 | 407 | 52 |
| Comparative | ||||||
| Example 1 | ||||||
| Additional | 80.1 | 87.0 | 69.7 | 11.0 | 419 | 64 |
| Comparative | ||||||
| Example 2 | ||||||
| Additional | 79.4 | 83.9 | 66.6 | 13.7 | 474 | 183 |
| Comparative | ||||||
| Example 3 | ||||||
| ΔT (° C.) : Difference between the maximum temperature inside a catalyst bed and the reaction temperature set during reaction | ||||||
As shown in Table 7, in the case of Additional Examples 1 and 2 in which silicon carbide and zirconia were used as the dilution filler, respectively, the maximum temperature inside a catalyst bed was equal to or lower than that of Additional Comparative Examples 1 and 2, and the conversion rate of butene, selectivity for 1,3-butadiene, and 1,3-butadiene yield were excellent.
In addition, when alumina having a packing density outside the range of the present invention was used as the porous support, it was confirmed that the effect of suppressing overheating of the catalyst bed was insufficient even though the catalyst was diluted and supplied to satisfy Equations 1 and 2, and that the conversion rate of butene and butadiene yield were significantly reduced. In particular, when the packing density was less than the lower limit of the present invention (Additional Comparative Example 1), it was confirmed that the conversion rate of butene and butadiene yield were significantly reduced.
In addition, when mixing of the porous support and the dilution filler was omitted, as shown in Table 7, it was confirmed that the temperature inside the catalyst bed was considerably high because heat generation was not effectively controlled, and selectivity for COx as a side reaction product was considerably increased. The lifespan of the catalyst is expected to be considerably short.
Referring to these results, when the catalyst system according to the present invention was used, heat generation was effectively controlled, and thus the temperature inside the catalyst bed was kept relatively stable. On the other hand, when the catalyst system of Additional Comparative Example 3 was used, it was confirmed that the temperature inside the catalyst bed was drastically increased at the beginning of reaction, and thereafter was drastically decreased.
According to the results of the experiments, when the catalyst system according to the present invention is used, heat generated inside a reactor can be effectively controlled. Thus, the present invention can provide a reaction system with a stable temperature gradient. In addition, even when the maximum temperature inside a catalyst bed is low, high reaction activity and stability can be provided. Therefore, the catalyst system of the present invention can improve the efficiency of oxidative dehydrogenation.
Claims (13)
1. A catalyst system for oxidative dehydrogenation, wherein a reactor is filled with a catalyst for oxidative dehydrogenation in an n-layer structure (n being an integer of 2 or more),
wherein the catalyst is diluted and the reactor is filled with the diluted catalyst so that each layer of the n-layer structure satisfies Equations 1 and 2 below:
X wt %+Y wt %+Z wt %=100 wt %, [Equation 1]
X wt %+Y wt %+Z wt %=100 wt %, [Equation 1]
wherein X represents an amount of AB2O4 and is 3 to 30, wherein A is one or more selected from the group consisting of copper (Cu), radium (Ra), barium (Ba), strontium (Sr), calcium (Ca), beryllium (Be), zinc (Zn), magnesium (Mg), manganese (Mn), cerium (Ce), zirconium (Zr), lanthanum (La), and cobalt (Co) and B is iron (Fe);
Y is an amount of a porous support and is 20 to 97; and
Z is an amount of one or more dilution fillers selected from alumina, silica, silicon carbide, zirconia, titania, and cordierite and is 0 to 77;
X n >X n−1, [Equation 2]
X n >X n−1, [Equation 2]
wherein, with respect to a direction in which reactants are fed into the reactor, Xn represents an amount of X for an n-th layer, and Xn−1 represents an amount of X for an (n−1)th layer; and
wherein the catalyst system satisfies Equation 5 below:
(Z n−1 −Z n)≥20, [Equation 5]
(Z n−1 −Z n)≥20, [Equation 5]
wherein Zn represents an amount of Z for the n-th layer, and Zn−1 represents an amount of Z for the (n−1)th layer.
2. The catalyst system according to claim 1 , wherein n is an integer of 2 to 8.
3. The catalyst system according to claim 1 , wherein the catalyst system satisfies Equation 3 below:
(X n −X n−1)≥2, [Equation 3]
(X n −X n−1)≥2, [Equation 3]
wherein Xn represents an amount of X for an n-th layer, and Xn−1 represents an amount of X for an (n−1)th layer.
4. The catalyst system according to claim 1 , wherein at least one of the n layers has a Z value greater than 0.
5. The catalyst system according to claim 1 , wherein, when at least one layer has a Z value other than 0, the catalyst system satisfies Equation 4 below:
(Yn−Yn−1)≥15, [Equation 4]
(Yn−Yn−1)≥15, [Equation 4]
wherein Yn represents an amount of Y for the n-th layer, and Yn−1 represents an amount of Y for the (n−1)th layer.
6. The catalyst system according to claim 1 , wherein AB2O4 is a coating catalyst coated on the porous support.
7. The catalyst system according to claim 6 , wherein the coating catalyst is a binder-free catalyst.
8. The catalyst system according to claim 1 , wherein AB2O4 is a zinc ferrite, wherein A is Zn and B is Fe.
9. The catalyst system according to claim 1 , wherein the porous support is one or more selected from the group consisting of alumina, silica, titania, zirconia, silicon carbide, and cordierite.
10. The catalyst system according to claim 1 , wherein the porous support has an average pore size of 50 to 200 μm.
11. The catalyst system according to claim 1 , wherein the porous support has a packing density of 0.8 to 1.5 kg/m3.
12. A catalyst system for oxidative dehydrogenation, wherein a reactor is filled with a catalyst for oxidative dehydrogenation,
wherein the catalyst is diluted and the reactor is filled with the diluted catalyst so as to satisfy Equation 6 below:
X wt %+Y wt %+Z wt %=100 wt %, [Equation 6]
X wt %+Y wt %+Z wt %=100 wt %, [Equation 6]
wherein X is an amount of AB2O4 and is 5 to 25 wt % wherein A is one or more selected from the group consisting of copper (Cu), radium (Ra), barium (Ba), strontium (Sr), calcium (Ca), beryllium (Be), zinc (Zn), magnesium (Mg), manganese (Mn), cerium (Ce), zirconium (Zr), lanthanum (La), and cobalt (Co) and B is iron (Fe);
Y is an amount of a porous support and is 25 to 85 wt %; and
Z is an amount of one or more dilution fillers selected from alumina, silica, silicon carbide, zirconia, titania, and cordierite and is 10 to 70 wt %.
13. A catalyst system for oxidative dehydrogenation, wherein a reactor is filled with a catalyst for oxidative dehydrogenation in an n-layer structure (n being an integer of 2 or more),
wherein the catalyst is diluted and the reactor is filled with the diluted catalyst so that each layer of the n-layer structure satisfies Equations 1 and 2 below:
X wt %+Y wt %+Z wt %=100 wt %, [Equation 1]
X wt %+Y wt %+Z wt %=100 wt %, [Equation 1]
wherein X represents an amount of AB2O4 and is 3 to 30 wt %, wherein A is one or more selected from the group consisting of copper (Cu), radium (Ra), barium (Ba), strontium (Sr), calcium (Ca), beryllium (Be), zinc (Zn), magnesium (Mg), manganese (Mn), cerium (Ce), zirconium (Zr), lanthanum (La), and cobalt (Co) and B is iron (Fe);
Y is an amount of a porous support having a packing density of 0.8 to 1.5 kg/m3 and is 20 to 97 wt %; and
Z is an amount of one or more dilution fillers selected from alumina, silica, silicon carbide, zirconia, titania, and cordierite and is 0 to 77 wt %;
X n >X n−1, [Equation 2]
X n >X n−1, [Equation 2]
wherein, with respect to a direction in which reactants are fed into the reactor, Xn represents X for an n-th layer, and Xn−1 represents X for an (n−1)th layer; and
wherein at least one of the n layers has a Z value greater than 0.
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| PCT/KR2018/014736 WO2019107884A1 (en) | 2017-11-30 | 2018-11-27 | Catalyst system for oxidative dehydrogenation reaction, reactor for butadiene production including same, and method for preparing 1,3-butadiene |
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| Publication number | Publication date |
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| US20200122126A1 (en) | 2020-04-23 |
| KR20190063551A (en) | 2019-06-10 |
| WO2019107884A1 (en) | 2019-06-06 |
| EP3556463A4 (en) | 2019-12-25 |
| CN110167669A (en) | 2019-08-23 |
| JP6812620B2 (en) | 2021-01-13 |
| EP3556463A1 (en) | 2019-10-23 |
| JP2020505219A (en) | 2020-02-20 |
| KR102262896B1 (en) | 2021-06-09 |
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